Production of alcohols



Patented July 21, I

- UNITED STATES.

2,048,882 7 mnUc'noN or mono s Martin Luther, Mannheim; and Wilhelm Dietrich,

01m n, Germany, assignorsto I. G. Farbenindnstrie Aktiengesellschaft, .Frankfort-on-thc- Main,

No Application mm 3, 1930, Serial Germany No. 488,280. In

October 15, 1929 1 cm (or. 260-156) The present invention relates to the production of alcohols. 1

By the destructive oxidation of liquid or solid hydro-carbons, a mixture of different oxygen-con- 5 taining products, such as acids, lactones, esters, aldehydes, ketones and the like which usually also contain unattached initial material is generally obtained as the oxidation product.- When obtained underthe said liquid-phase conditions; the 0 oxygenated products of the liquid-phase oxidation will contain about the same number of carbon atoms as the initial materials, of which paraflln is known to contain hydrocarbons containing from about 12 to 36 carbon atoms, mainly from about 15 12 to about'24 carbon atoms (compare for ex- 1 ample Berichte der peut'schen Chemischen Gesellschaft, vol. 40, (1907) page 4779) In accordance with the said statements water-insoluble fatty acids containing from 10 to about 35 carbon atoms,

l) mainly from 11 to 24 carbon atoms, have been identified in the liquid phase oxidation products from paraiiln (according to the aforesaid citations, Chemiker Zeitung 49 (1920) page 311, and Zeitshrift fur angewandte Chemie 1918, page 691-. 35 Similarly, alcohols in the said oxidation products contain from about 10 to 25 carbon atoms (see Journal of the Chemical Society 1926, page 2377) lauryl, myristyl, palmityl and stearyl-or octodecyl alcohols together with alcohols containing 22, 24-

and 25 carbon atoms having been found besides the corresponding myristic, palmitic, isopalmitic,

stearic and arachic acids, the alcohols havingfrom about 12 to about 20 carbon atoms constituting generally the predominant portion ,of the 35 whole mixture of alcohols.

we have now found that a product consisting mainly of the higher members of the aliphatic alcohol series is readily obtained fromthe mixture produced in the manner already known by the dei structive oxidation of difllcultly volatile, i. e. liquid or solid hydrocarbons in the liquid state as for example with gaseous oxidizing agents containing free oxygen such as air or mixtures of oxygen with carbon dioxide or nitrogen, with or without the 45 employment of catalysts, by subjecting the said mixture obtained by oxidation, .or constituents containing oxygen separated therefrom, as for example the neutral fraction consisting oi: esters, ketones and the like, to a hydrogenation at super- 50 atmospheric pressure with large quantities of hydrogen, or gaseous mixtures containing hydrogen, The hydrogenation is carried out with hydrogen -at elevated Pres usually ranging up to about 100 atmospheres, in the-presence of a hydrogenat- 5 ing catalyst, asfor exampleflnely divided metallicv nickel, and at elevated temperatures ranging from about I50to 230 0., but somewhat higher or lower temperatures such as up to about 250 and down to about 100 C. may also be employed. The pressure employed should generally exceed 10 at- 5 mospheres since otherwise, the reaction would proceed too slowly for practical purposes and pressures above 300 atmospheres are generally not employed since this method of working would require particularly costly apparatus. The absorption of hydrogen is completed-in a short period of time. The duration 'ofthe reaction depends .on the kind of the initial material and on I the working conditions employed. For example with oxidation products from paraffln wax a hy- 15 drogenation efiected at 200 C, and at a pressure of 50 atmospheres in the presence .of nickel as a catalyst is already completed in three hours. The

.separation of the alcohols formedfrom the unat- Though the initial oxidation products are of a Q most heterogeneous composition the reduction stops against all expectation at the alcohol stage and practically no hydrocarbons are formed.

Alcohols having a more or less high melting point are obtained according to the nature of the initial materials employed for the oxidation, such as petroleum fractions boiling above, 180 0., as for example middle oils, liquid, hard or soft paraffins and the. like. For example, by employ ng hard paramn wax as the initial material in the oxidation, a product is obtained the melting point of which is above 30 C. In most cases mixtures of alcohols having a very high molecular weight are obtained, the alcohols from oxidation products of the said petroleum fractions containing an average of about 10 carbon atoms and those from paraflin waxes an average of about 15 carbonatoms.

. Depending on the content'of the initial materials a for the hydrogenation of 'un'oxidized hydrocarbon -t he hydroxyl value of the final products will vary Example 1 700 parts of the neutral oxygen-containing constitutents separated from an oxidation product 65 which appears from the following figures:

2 Y, r a,o4s,eea,

obtained by treatment of hard paramn waxwith air at a temperature 01 about 160 C. and containing from about 35 to 40 per cent of oxygenated constituents having a neutral reaction are treated 5 for some hours in a stirring autoclave with hy- -drogen-at 200C. under a pressure or 30 atmospheres inthe presence of finely divided metallic nickel, and in this manner 5 parts of hydrogen are absorbed." The nickel catalyst is then filtered oil. A pure white mixture consisting of higher wax alcohols is obtained and may be fiurther purified by the usual methods, as for example by steam distillation. The mixture has hydrophilous properties and is eminently suitable for the prepa- ,ration oi. ointments, esters, sulphonation products tor wetting and cleansing agents and the like.

' The hydroxyl value of this mixture of alcohols amounts to from about 120 to 130.

' k i v Example 2 1 1000 parts or an 'oxidation product which has been prepared by blowing paraiiln oil in the presence oi. 1 per cent its weight of manganese naphthenate at 160 C. with air and which contains about 35 per cent its weight of free carboxylic acids, are subjected in an autoclave and in the presence of 5 partsot nickel deposited'on 15 parts v 01 kieseiguhr to.-the action of hydrogen at a temperature of 180C. for 4 hours while stirring,atter hydrogen has been pressed into the autoclave until a pressure of 50 atmospheres has been at-1 tained. Alter flitering'oi! the catalyst the last traces oi nickel are washed out from .the product by means 6! dilute sulphuric ,acid. After separating the saponiflable constituents of the products bya treatment with aqueous caustic soda at about 100 C. and drawing 01! the aqueous soap solution, about 30 per cent of the original oxidation product is obtained as a mixture of 40 high-molecular liquid alcohols which has a hydroxyl value of 160;

' Example 3 4 I o l 1000 parts or an-oxidation product'prepared by blowing hard parailln wax with air at about 160 C. are treated with hydrogen at 250 C.. and atmospheres pressure in an autoclave ai'ter adding 10 parts of nnely divided cobalt which has been prepared by heating cobalt carbonate Ai'ter filtering of! the catalyst the product 'is washed with dilute aqueous sulphuric acid for re-" moving traces of cobalt from the reaction prodnot. After separating saponiflable constituents (free acids, 'lactones' and esters) from the reaction product a semi-solid mixture or alcohols is obtained in a yield of per cent of the'original oxidation product, which may find useful application in the production of salves or ointment's or I M for theproduction of wetting, cleansing or emulsii'y s a e by v o By the aioredescribed treatment to per cent by weight of the esters and tree acids' contained in the oxidation product are converted intoalcohols Um i- Hrdroxyl Add Baponiiicaflable m tueoiun .vnlus tionvalue taunt saponiii- 1 v cent) sblematter v Initial W..-" 78.5 143.! 47.0 15.3 leaotio rprodnot 1s.s as 66.2 lots trample! icon and or an oxidation product, prepared by in a current 01' hydrogen at '350" C. for 36 hours;

blowing paramn oil in the presence of 1 per cent I its weight oi manganese naphthenate' with air at .160 C. and which contains about 35 per cent by,

weight of free carboxylic acids is heated, while stirring, together with 5 parts of nickeldeposited 5' on 15 parts otkieselguhnat 180 C.-and 50 atmospheres which pressure is attained'by pressing hydrogen into the autoclave; ,Aiter'tiltering oi! the catalyst any traces or nickel in the reaction prod uct are washed away with the aid oi dilutesull0 phuric acid. After separating oil the saponiflable constituents (free acids, lactones and esters) a mixture of high molecular liquid alcohols is ,obtainedin a yield of about 30 per cent of the original oxidation product. 15 I Q Example 5 1000 parts of an oxidation product prepared by blowing soft paraflln wax at about 150 C. with q air, trom which free carbowlic acids have been 20 removed with the aid of aqueous soda solution, are mixed with 5 parts of nickeldeposited on 15 parts of kieselguhr and the whole is then heated !or tour hours at 200 C.,inan autoclave while stirring .ai'ter hydrogen has, been pressed into the latter until a pressure of 60.atmospheres is attained. The nickel catalyst is then filtered of! and after separating the saponiflable constituents (esters,

,lactonestand acids) a mixture of semi-solid hig molecular alcohols is obtained which e a hydroxyl value of 140. I

Whatweclaimis;--

1. The process torthe production of prodl'ictl consisting mainly of ot the highermembers of the aliphatic alcohol series which 35 comprises heating the products, comprising nonaromatic long-chain acids, esters and carbonyl compounds from a destructive oxidation of tilt:- flcultly volatile hydrocarbons in" the liquid phase by means 01 a gaseous oxidizing agent contain- 40 ing tree oxygen, in the presence or hydrogen and ot a hydrogenatirig catalyst containing an ele-'- ment selected iromtheiron'group at a pressure above atmospheric pressure.

2. The processi'or the production of 45 consisting mainly of mixtures of the higher members or the aliphatic alcohol series which comprises heating the produetspoomprising non-aromatic long-chain acids, 'estersand carbonyl compounds from a destructive oxidation or dimei itiy 50 volatile hydrocarbons in the liquid phase by 4 means or a gaseous oxidizing agent containing 'i'ree oxygen, in the presence of hydrogen and of a hydrogenating catalyst selected from the iron group ata pressure above 55 atmospheric pressure to a temperature between 1 about and 250C.

3. The processior the production of products mainly of mixturesoi the'higher members or the aliphatic alcohol series which comprises heating the products, comprisingnonaromatic long-chain acids, esters and carbonyl compounds from a destructive oxidationot diiii-. cultly volatile paramn hydrocarbons in the liquid phase by means 01 air, in the presence of hydrogen and of ahydrogenating catalyst containing an element selected iron the iron group at a pressure above atmospheric pressure toa temperature between about and 230 C. I

4. The process tor "the production oi' products consisting mainly of. mixtures of the higher members of the aliphatic alcohol series which comprises heating the products, comprising nonaromatie long-chain acidsjestersand carbonyl 75 compounds from a destructive oxidation of amcultly volatile paramn hydrocarbons in the liquid phase by means or air, in the presence of hydrogen and of nickel at a pressure above 10 atmos- I pheres to a temperature between about about 150 and 230 C.

5. The process for the production of products I consisting mainly of mixtures of the higher members of the aliphatic alcohol series which comprises heating the products, comprising nonaromatic long-chain acids.- esters and carbonyl compounds from a destructive oxidation of paraflln wax in the liquid phase by means of air, in the presence of hydrogen and of nickel at a pressure between about 20 and 100 atmospheres.

6. The process Iorthe production of products consisting mainly oi. mixtures of the higher members of the aliphatic alcohol series which comprises heating a fraction of reducible neutral compounds of a product, comprising long-chain esters, and carbonyl compounds from a destructive oxidation of paraflln wax in the liquid phase by means or air, in the presence or hydrogen and of nickel at a pressure between about 20 and 100 atmospheres.

7. Mixtures of alcohols having hydroxyi values between 100 and 200 the said alcohols having an average of carbon atoms between 10 and 15, obtained by the catalytic hydrogenation of products from the destructive oxidation of difllcultly 

